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DEPARTMENT OF CHEMISTRY VIKRAMA SIMHAPURI UNIVERSITY: NELLORE – 524 004 VSURESET CHEMISTRY Ph.D. ENTRANCE TEST SYLLABUS & MODEL QUESTIONS SECTION - B CO-ORDINATION COMPOUNDS Introduction to Crystal field Theory, CFSE and its calculation, Paring energy, Splitting of ‘d’ orbitals in Trigonal bi pyramidal, square planar, square pyramid and pentagonal bipyramidal geometries, Jahn –Teller effect, Application of CFT, OSSE, site Selection in Spinels, Short comings of CFT, Evidence for covalency –Nephelauxetic effect. MOT of co-ordinate Bonds –M.O. Diagrams for octahedral, tetrahedral and square planar complexes.. REACTION MECHANISMS IN COMPLEXES Reactivity of metal complexes –inert and labile complexes- kinetics and Mechanisms of substitution reactions –Substitution reactions in octahedral complexes- Acid Hydrolysis factors affecting Acid Hydrolysis - Base Hydrolysis-conjugate Base Mechanisms Anation Reactions -Substitution Reactions in Square Planar complexes- Trans effect – Mechanisms of Trans effect –Electron Transfer Reaction-Inner Sphere and outer Sphere Mechanisms- Marcus theory. TRANSITION METAL Π – COMPLEXES Transition metal π – complexes with unsaturated organic molecules – alkenes, alkynes, diene, dienyl and arene complexes-general methods of preparation, properties, nature of bonding and structural features – Important reactions relating to Nucleophilic and Electrophilic attack on ligands and to organic synthesis. ELECTRONIC SPECTRA OF COMPLEXES Frank-Condon principle – Russel-Saunders coupling – Spectroscopic term symbolsSelection rules – Break – down of selection rules –Orgel Diagrams for d1 to d9 configurations in Octahedral and tetrahedral fields. Tanabe – Sugano diagrams of d2 to d8 1 configurations. – Spectra of octahedral and tetrahedral complexes of metal ions of d to d9 configurations. –Calculation of Dq and B1 parameters –Charge transfer spectra. Differences between ligand field spectra and charge transfer spectra. MAGNETIC PROPERTIES OF TRANSITION METAL COMPLEXES Diamagnetism and paramagnetism-orbital and spin contributions, spin-orbit coupling, Hunds third rule and Energies of J levels – Curie law and Curie – Weiss law- Ferromagnetism and antiferromagnetism – Temperature independent magnetism – Magnetic – Paramagnetism and crystalline fields – Ti (III), V (III), VO2+, Cr (III), Mn (II), Fe (III), Co(II), Ni (II) and Cu (II). Magnetic Exchange in copper acetate and other dimmers – spin cross over in complexes. SPECRAL TECHNIQUES OF INORGANIC COMPLEXES Mossbauer spectroscopy, NQR spectroscopy, Electron spin resonance spectroscopy, photo electron spectroscopy AliphaticNucleophilic substitutions and Aromatic Nucleophilic substitutions VSURESET CHEMISTRY Ph.D. ENTRANCE TEST SYLLABUS & MODEL QUESTIONS Page 1 of 6 Addition to Carbon - Carbon Multiple Bonds: Addition to Carbon - Hetero Multiple Bonds: Elimination reactions, esterification and hydrolysis Reagents in organic synthesis Stereochemistry and conformational analysis Optical isomerism: Conformational analysis Reactive intermediates METHODS OF ORGANIC SYNTHESIS Oxidations: (i) Alcohols to carbonyls-Chromium (iv) oxidants-Dimethyl sulfoxide oxidation, periodate oxidation, Oppenauer oxidation, oxidation with manganese ioxide, oxidation with silver carbonate (ii) Alkenes to epoxides-peroxide induced epoxidations. (iii) Alkenes to diols-oxidation with potassium permanaganate, osmium tetraoxide, Prevost reaction (iv) Ketones to esters-Bayer-villiger oxidation (v) Oxidative bond cleavage-cleavage of alkenes by transition metals. (vi) Oxidation of alkyl or alkenyl fragments-selenium dioxide and chromium trioxide oxidations. Reductions: Reduction with lithium aluminium hydride, sodium borohydride, alkoxides, bismethoxy ethoxy aluminium hydride, Boron aluminium hydride and derivatives-catalytic hydrogenation-dissolving metal reductions, Non-Metallic reducing agents including enzymatic and microbial Organometallic reagents: Synthesis and applications of Grignard reagents - Organolithium, Zinc, Copper, Mercury, Palladium, Rhodium and Nickel compounds in Organic synthesis - Homogeneous catalytic reactions - Hydrogenation, Hydroformylation. APPLICATION OF SPECTRAL TECHNIQUES TO ORGANIC COMPOUNDS Ultra violet &Visible Spectroscopy, ORD, Circular Dichroism, Infrared Spectroscopy Nuclear magnetic resonance spectroscopy (1h nmr), 13C NMR spectroscopy, mass spectrometry QUANTUM CHEMISTRY -I Introduction to Exact Quantum Mechanical Results: Operator algebra. Eigen values and eigen functions. Operators for momentum and energy. The derivation of Schrodinger equation and the postulates of Quantum Mechanics. Discussion of solutions of the Schrodinger equation to some model systems, viz., particle in a box, harmonic oscillator, rigid rotor, hydrogen atom Approximate Methods: The Variation Theorem, Linear variation Principle, Perturbation Theory (first Order and non-degenerate), Application of Variation Method and Perturbation Theory to the helium atom. PHASE RULE Stokes and Roozeboom plots. Three component liquid systems – formation of one pair, two pairs and three pairs of partially miscible liquids; two salts and water – no chemical combination, double salt formation, one salt forms hydrate and two salts form hydrates. .THERMODYNAMICS: Terms of Fugacity and its determination, partial molar properties, chemical potential, derivation of Gibbs-Duham’s equation, significance of partial molar properties, determination of partial molar volume. VSURESET CHEMISTRY Ph.D. ENTRANCE TEST SYLLABUS & MODEL QUESTIONS Page 2 of 6 Concept of distribution, thermodynamic probability and most probable Distribution – Ensemble averaging, Postulates of ensemble averaging, canonical, grand canonical and micro-canonical ensembles. Partition functions – traslational, rotational, vibrational and electronic partition functions, calculation of thermodynamic properties in partition functions Heat capacity, chemical equilibria and equilibrium constant in terms of partition functionsEntropy of monotomic gases (Sackur-Tetrade equation) ELECTROCHEMISTRY Irreversible Electrode Phenomenon: Reversibility and irreversibility, Dissolution and deposition potentials, Decomposition voltage, overvoltage, diffusion overvoltage, charge transfer overvoltage, reaction overvoltage, concentration overvoltage-hydrogen and oxygen overvoltages, Tafel plots, Exchange current density and Transfer coefficient, Butler-Volmer equation for one electron transfer processes. Polarography: Theory of polarography, diffusion current, Ilkovic equation, Equation for half -wave potentials for reversible system when oxidant alone, reductant alone and both are present. SYMMETRY AND GROUP THEORY Symmetry Elements and Symmetry operation, Definitions of a group, sub-group, Relation between orders of a finite group and its sub-group-Conjugacy Relation and classes- point symmetry group, Schonflies symbols-Representation of groups by matrices (representation for Cn, Cnv, Dnh, etc. groups to be worked out explicitly), character of a representation. The great orthogonality theorem (without proof)- Character tables. POLYMERS- STRUCTURE AND PROPERTIES Morphology and order in crystalline polymers, configuration of Polymer chains, crystal structures and polymers, Stain induced morphology, morphology of chrystalline polymers, crystallization and melting- polymer structure and physical properties, crystalline melting point, Tm-melting point of homogeneous series, effect of chain flexibility and other steric factors- entropy and heat of fusion, the glass transition temperature, Tg , relationship between Tm and Tg effects of molecular weight, diluents, chemical structure, chain topology, branching and cross linking. ELECTRON DIFFRACTION: Scattering intensity Vs scattering angle, Wierl equation, Measurement techniques, Elucidation of structures of simple gas phase molecules, Low energy electron diffraction (LEED) for the study of surfaces. VSURESET CHEMISTRY Ph.D. ENTRANCE TEST SYLLABUS & MODEL QUESTIONS Page 3 of 6 MODEL QUESTIONS VSURESET-2014 Time: 2 Hours Max. Marks: 120 (Each question carries 1 mark the candidate has to answer 30 questions from Section A Carrying in 30 marks and 90 questions from Section B carrying 90 marks) 1. 2. 3. 4. 5. SECTION – A (GENERAL APTITUDE) 196, 256, 324, 400, 484 ______________ A) 576 B) 441 C) 529 D) 625 1/9, 2/27, 8/81 __________ 124/729 A) 32/243 B) 128/ 243 C) 256/ 243 D) 64/243 A man walks 30m towards of south then turning to his right, he walks 3m then turning to his left, he walks 2 m, again he turns to his left and walks 30m how far is the from his initial position. A) 20m B) 30m C) 60m D) 50m 64, 16:: 70;A) 17.5 B) 18.5 C)21.5 D) 20.5 Solve the given equation X2 - y2 = 34 X2 - y2 = 544 The value of X and Y are 6. A) ±4 , ±3 B) ±5, ±3 C) ±3, ±5 D) ±3, ±4 Mathematical standard deviation is represented by B) 7. ___________ __________ N N 2 2 C) D) __________ _________ N N2 Which of the following is not an internet Browser ? A) Internet Explorer B) Netscape C) Opare VSURESET CHEMISTRY Ph.D. ENTRANCE TEST SYLLABUS & MODEL QUESTIONS D) AQL Page 4 of 6 8. Data transfer rate in modems is measured in A) Bits for minute B) Bits for Second C) Bond width D) None of the above Basics of steps of research process includes A) Problem definition B) Research design C) Data collection D) All Which of the following comes under quantitative objective o research A) A Study of estimate the demand of product B) A Study of testing the effect of level of education C) A Study on the impulse buying behavior of customers D) None. 9. 10. . . . 30. SECTION-B (CHEMISTRY) 31) Carbonyl Compounds can be converted into alkene by the following reaction a) Wittig reaction b) Clemmensen reduction c) Wolf – Kishner reduction d) None of the Above 32) In NMR-H1 the aldehydic proton can observed at a) 8 PPm b) 6 PPm c) 9 PPm d) 12 PPm 33) Calamine is the ore of a) Aluminium b) Zinc c) Iron d) Copper 34) How many ions are produced from complex Co(NH3)6Cl2 in solution a) 6 b) 4 c) 3 d) 2 35) During an isothermal expansion of an ideal gas its: a) Internal energy increases b) Enthalpy decreases c) Enthalpy remains unaffected d) Enthalpy reduces to Zero 36) If the initial concentration of the reactant is doubled, time for half reaction is also doubled, the order of reaction is a) Zero VSURESET CHEMISTRY Ph.D. ENTRANCE TEST SYLLABUS & MODEL QUESTIONS Page 5 of 6 b) First c) Second d) Third . . . . . 120) VSURESET CHEMISTRY Ph.D. ENTRANCE TEST SYLLABUS & MODEL QUESTIONS Page 6 of 6